EP0469545B1 - Catalyseur d'amine pour la production de mousses de polyuréthane et procédé de production de mousses de polyuréthane - Google Patents

Catalyseur d'amine pour la production de mousses de polyuréthane et procédé de production de mousses de polyuréthane Download PDF

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Publication number
EP0469545B1
EP0469545B1 EP91112793A EP91112793A EP0469545B1 EP 0469545 B1 EP0469545 B1 EP 0469545B1 EP 91112793 A EP91112793 A EP 91112793A EP 91112793 A EP91112793 A EP 91112793A EP 0469545 B1 EP0469545 B1 EP 0469545B1
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EP
European Patent Office
Prior art keywords
polyurethane
amine
catalyst
polyurethane foams
materials
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91112793A
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German (de)
English (en)
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EP0469545A3 (en
EP0469545A2 (fr
Inventor
Yutaka Tamano
Masaki Ishida
Shuichi Okuzono
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
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Tosoh Corp
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Publication date
Priority claimed from JP2199268A external-priority patent/JPH0747619B2/ja
Priority claimed from JP3188280A external-priority patent/JPH0739456B2/ja
Application filed by Tosoh Corp filed Critical Tosoh Corp
Publication of EP0469545A2 publication Critical patent/EP0469545A2/fr
Publication of EP0469545A3 publication Critical patent/EP0469545A3/en
Application granted granted Critical
Publication of EP0469545B1 publication Critical patent/EP0469545B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density

Definitions

  • the present invention relates to an amine catalyst for producing flexible, semi-rigid and rigid polyurethane foams, or elastomers comprising polyurethane foams. More particularly, the present invention relates to an amine catalyst which has a secondary hydroxyl group in the molecule and exhibits non-bleeding properties to the polyurethane resin which is excellent in moldability. It also relates to a process for the production of a polyurethane foam using the catalyst.
  • Polyurethane foam is usually produced from a polyol and a polyisocyanate mixture containing a catalyst, foaming agents(halogenated hydrocarbonsand/or water), and if necessary, other auxiliary agents,by instantaneously stirring and mixing them to promote foaming.
  • the polyurethane foam is advantageously used in materials for various articles because of its light weight and its excellent cushion property, anti-shock property, anti-vibration property, and other advantageous properties.
  • amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine and tetramethylhexamethylenediamine, have been employed as catalysts for producing these polyurethanes to achieve a good moldability of the resulting foams.
  • amine catalysts encounters various problems when the catalysts are used in the production, for example, of interior articles of automobiles (such as instrument panels, seats, head rests and arm rests which are produced by using polyurethane foam together with other materials (such as polyvinylchloride resin, ABS resin and polycarbonate resin) either in a combined form (such as in foils, coatings and in border materials), or by being molded such that it will be integrated into these materials.
  • an amine catalyst remaining in a polyurethane foam may migrate to other materials which are in contact with the polyurethane foam. This will cause deterioration and discoloration of the resultant other materials, and hence it reduces the commercial value of the product.
  • amine catalysts work in such a way that they accelerate the reaction which leads to the polyurethane foam formation, and at the same time they react with the raw material polyisocyanate due to the presence of reactive groups in the molecule so that they stay fixed to the polyurethane resin. Therefore, problems of deteriorated physical properties and discoloration of the resultant products can be avoided because the amine catalyst does not migrate to other materials in contact with the polyurethane foam.
  • the amine catalysts having reactive groups lose their catalytic activity during the reaction if they are entrapped in the polyurethane resin. This results in an incompiete formation of the final polyurethane resin. Thus, problems of an increased percentage of reject products having voids in the polyurethane foam and a deteriorated moldability have been reported.
  • GB-A-2 094 784 discloses a catalyst including a structure having two tertiary amines linked by a carbon chain of three carbon atoms and a primary or secondary hydroxyl group.
  • amine catalysts For the production of articles from polyurethane foam either in combination with or molded to be integrated with other materials, such amine catalysts are desired which are of a non-bleeding type so that they do not cause a deterioration nor a discoloration of other materials which are brought into contact with the catalyst and, in addition, render an excellent moldability to the polyurethane.
  • the present inventors continued comprehensive investigations for amine catalysts which are suited for producing such a polyurethane and for a method for its production.
  • the present inventors have found that the claimed amine catalysts having a secondary hydroxyl group in the molecule exhibit non-bleeding properties in the polyurethane resin, lose less catalytic activity during the polyurethane formation reaction, and do not deteriorate nor discolor other materials in contact with the polyurethane foam when the catalyst is used for making products made of polyurethane foam by combining it or by molding it integrated with other materials.
  • the present invention thus provides amine catalysts exhibiting non-bleeding properties in a polyurethane resin. They are advantageously used for producing a polyurethane foam with excellent moldability, and also in a process for producing polyurethane foams.
  • the present invention provides amine catalysts for producing polyurethane foams comprising a compound expressed by the following general formula (I) and a process for the production of the polyurethane foams therewith, (in the formula, n is an integer from 1 to 3, and R 1 , R 2 and R 3 respectively and independently stands for an alkyl group having 1 to 3 carbons).
  • the amine catalyst of the present invention is a tertiary amine compound having a secondary hydroxyl group in the molecule expressed by the general formula (I) above.
  • the amine catalysts of the present invention include preferably N,N,N'-trimethyl-N'-(2-hydroxypropyl)ethylenediamine, N,N,N',N"-tetramethyl-N"-(2-hydroxypropyl )diethylenetriamine and N,N,N',N",N"'-penta-methyi-N"'-( 2-hydroxypropyl)triethylenetetramine.
  • N,N,N'-trimethyl-N'-(2-hydroxypropyl)-ethylenediamine, and N,N,N',N"-tetramethyl-N"-(2-hydroxypropyl)-diethylenetriamine are more preferred.
  • amine catalysts may be prepared according to a process which is known in the art.
  • the preparation may be performed by the Leuckart-Wallach reaction, as disclosed in U.S. Patent No. 4,026,840, starting from a corresponding alkanolamine, and by use of a reductive alkylation reaction as disclosed in West German Patent No. 2,618,580.
  • the amount of the amine catalyst of the present invention for producing polyurethane is in the range from 0.02 to 10 parts, more preferably 0.1 to 5 parts by weight based on 100 parts of the polyol.
  • other known tertiary amine catalysts, organic carboxylic acid salts thereof, and organic tin compounds which are usually used as cocatalysts may be employed as auxiliary catalyst as long as the proper catalytic function of the catalysts of the present invention is not lost.
  • triethylenediamine can be preferably used because it does not impair the good moldability of the amine catalyst of the present invention and does not deteriorate nor discolor the materials which said catalyst contacts for a long time.
  • amine catalyst (I) of the present invention particularly desirable is the combined use of the amine catalyst (I) of the present invention and triethylenediamine (II) in the ratio ((I)/(II)) by weight being not less than 0.75 and not larger than 12.
  • polyols, polyisocyanates, and foaming agents, stabilizers, and if necessary, other auxiliary agents which are hitherto known may be employed.
  • Polyols include polyetherpolyols, polymer polyols, and polyesterpolyols having 2 or more reactive hydroxyl groups.
  • the polyetherpolyols include, for example, polyhydric alcohols such as glycol, glycerin, pentaerythritol, and sucrose; and/or a polyetherpolyol obtained by adding ethylene oxide or propylene oxide to a mixture of aliphatic amine compounds such as ammonia, and ethyleneamine; aromatic amine compounds such as toluene diamine, and diphenylmethane-4,4'-diamine.
  • the polymer polyol is exemplified by a reaction product of said polyetherpolyol with an ethylenic unsaturated monomer, such as butadiene, acrylonitrile, and styrene, the reaction being conducted in the presence of a radical polymerization catalyst.
  • Polyesterpolyols include those which are produced from a dibasic acid and a polyhydric alcohol such as, for example, polyethyleneadipate and polyethyleneterephthalates which may include those products reclaimed from waste materials.
  • organic polyisocyanates may be employed including, for example, aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymerized isocyanates thereof; aliphatic polyisocyanates such as hexamethylenediisocyanate ; alicyclic polyisocyanates such as isophoronediisocyanate ; prepolymers with terminal isocyanate groups such as toluenediisocyanate prepolymers and diphenylmethane-4,4'-diisocyanate prepolymerswhich are obtained by the reaction of the above-mentioned substances with a polyol; denatured isocyanatessuch as carbodiimide denatured substances; and further mixed polyisocyanates thereof.
  • aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, polymerized isocyan
  • Foaming agents are exemplified by halogenated hydrocarbons of lower boiling points and/or water.
  • halogenated methanes and halogenated ethanes may be used as halogenated hydrocarbons.
  • chlorofluorocarbon compounds such as trichloromonofluoromethane (R-11), dichlorotrifluoroethane (R-123), dichloromonofluoroethane (R-141b), are preferred.
  • the amount of the substances to be used is not particularly limited, but the amount of the chlorofluorocarbon compound to be used is usually not larger than 35 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts of the polyol, and the amount of water to be used is not less than 2.0 parts, preferably 3.0 to 20.0 parts.
  • the stabilizer is selected, for example, from non-ionic surfactants such as organopolysiloxane-polyoxyalkylene copolymers and silicone-glycol copolymers, or a mixture thereof.
  • the amount of the stabilizer is not particularly critical, but usually 0 to 2.5 parts by weight are used per 100 parts by weight of polyol.
  • auxiliary agents may be added if necessary. They include flame retardants, coloring agents, fillers, oxidation-preventors and ultraviolet ray screening agents.
  • the polyurethanes prepared by the use of the amine catalysts of the present invention include flexible foams, HR foams, semi-rigid foams, rigid foams, microcellular foams, and elastomers which are prepared by the conventional known one-shot method and the prepolymer method.
  • the process for producing a polyurethane foam by using a foaming agent which is processed in a combined form with other materials, such as foil, coating, or border material, or by molding integratedly with other materials is particularly preferred.
  • Said other materials referred to above include resins such as polyvinylchloride resins, ABS resins, polycarbonate resins, metals, and glasses.
  • Examples of applications of the product include interior articles of automobiles such as instrument panels, seats, head rests, arm rests, and door panels as well as packaging materials.
  • the amine catalyst of the present invention behaves as a catalyst of the non-bleeding type in the polyurethane resin because it has a secondary hydroxyl group in the molecule. Also its moldability is excellent since it suffers little from decrease in the catalytic activity during the polyurethane forming reaction, when compared with other reactive catalysts. The result is that the amine catalyst of the present invention, when it is used for the production of articles from the polyurethane foam in combination with, or by being molded integratedly with other materials, provides products with a lower rate of poor quality product formation and without deteriorating and discoloring other materials which are brought into contact with the polyurethane.
  • Density was measured of a test specimen prepared by cutting the central portion of the foam in a size of 6 x 6 x 6 cm.
  • Voids generated at the bottom portion of a foam formed were observed and rated in 3 grades: Large voids .... ⁇ Small voids .... ⁇ No void .... ⁇
  • a starting material of polyurethane was poured onto a sheet of polyvinylchloride resin (GA-20, made by Plus-tech Co.) placed at the bottom of an aluminum mold (with the dimension of 12 x 50 x 2 cm) which was adjusted to 40°C, to prepare a test piece for the discoloration test.
  • the specimen was heated to 120°C in an oven, and the rate of discoloration after 200 hours was measured with a color meter (made by Nippon Denshoku Co.), to obtain the color difference value ( ⁇ E; difference from the blank value).
  • the amine catalyst of the present invention exhibited a small value of discoloration and further improved moldability.
  • the amine catalysts in Comparative Examples 1 to 3 showed worse moldability, though the discoloration values were small, while the amine catalysts in Comparative Examples 4 and 5 had large discoloration values. Thus, the catalysts in the Comparative Examples could not be used.

Claims (5)

  1. Catalyseur d'amine destiné à la production d'une mousse de polyuréthane comprenant un composé exprimé par la formule générale suivante (I) :
    Figure imgb0005
     (dans la formule, n est un nombre entier de 1 à 3 et R1, R2 et R3 représentent respectivement et indépendamment des groupes alkyle comportant 1 à 3 atomes de carbone).
  2. Procédé de production d'une mousse de polyuréthane consistant à faire réagir un polyol avec un polyisocyanate en présence d'un catalyseur et d'un agent moussant, comprenant l'utilisation du catalyseur d'amine selon la revendication 1.
  3. Procédé selon la revendication 2, dans lequel on moule ultérieurement ladite mousse de polyuréthane puis on la traite de manière à ce qu'elle soit combinée avec d'autres matériaux ou leur soit intégrée.
  4. Procédé selon la revendication 2 ou 3, dans lequel l'agent moussant est l'eau et/ou un hydrocarbure halogéné.
  5. Procédé selon la revendication 3, dans lequel ledit autre matériau comprend un ou plusieurs matériaux choisis dans le groupe constitué d'une résine de poly(chlorure de vinyle), d'une résine ABS et d'une résine de polycarbonate.
EP91112793A 1990-07-30 1991-07-30 Catalyseur d'amine pour la production de mousses de polyuréthane et procédé de production de mousses de polyuréthane Expired - Lifetime EP0469545B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2199268A JPH0747619B2 (ja) 1990-07-30 1990-07-30 ポリウレタン製造用アミン触媒及びポリウレタンの製造法
JP199268/90 1990-07-30
JP188280/91 1991-07-03
JP3188280A JPH0739456B2 (ja) 1991-07-03 1991-07-03 ポリウレタン製造用アミン触媒組成物及びポリウレタンの製造法

Publications (3)

Publication Number Publication Date
EP0469545A2 EP0469545A2 (fr) 1992-02-05
EP0469545A3 EP0469545A3 (en) 1992-09-16
EP0469545B1 true EP0469545B1 (fr) 1996-10-09

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US (1) US5374666A (fr)
EP (1) EP0469545B1 (fr)
DE (1) DE69122574T2 (fr)

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ES2208201T3 (es) 1999-10-13 2004-06-16 Tosoh Corporation Composicion de un catalizador para la preparacion de una resina de poliuretano y procedimiento para la preparacion de una resina de poliuretano.
CN1197890C (zh) 1999-12-17 2005-04-20 花王株式会社 聚氨酯的制造方法
US6534555B1 (en) 2001-09-10 2003-03-18 Huntsman Petrochemical Corporation Catalyst systems for polyurethane polyester foams
KR20030036060A (ko) 2001-10-31 2003-05-09 토소가부시키가이샤 유연 폴리우레탄폼의 제조방법
US20050059749A1 (en) * 2003-09-16 2005-03-17 Huntsman Petrochemical Corporation Catalysts useful in polyurethane foam
US8501828B2 (en) 2004-08-11 2013-08-06 Huntsman Petrochemical Llc Cure rebond binder
US20060141239A1 (en) * 2004-12-28 2006-06-29 Gilder Stephen D Method for making a bonded foam product suitable for use as an underlayment for floor coverings
EP2247638A1 (fr) * 2007-12-20 2010-11-10 DSM IP Assets B.V. Copolymères à blocs de polyuréthane hybrides avec une aptitude au traitement thermoplastique et des propriétés thermodurcies
US7872055B2 (en) * 2008-12-11 2011-01-18 Air Products and Chenicals, Inc. Catalyst composition for water blown, low density, rigid polyurethane foam
RU2562608C2 (ru) 2010-04-29 2015-09-10 Фаэрстоун Билдинг Продактс Компани, Ллк Экструдируемая самоклеящаяся адгезивная композиция и способы ее получения
EP2638122B1 (fr) 2010-11-12 2018-03-28 Firestone Building Products Company, LLC Composition adhésive non-noire autocollante et procédés pour préparer celle-ci
EP2690118A1 (fr) * 2012-07-27 2014-01-29 Basf Se Polyuréthane contenant des composés phosphorés
CN109456455B (zh) * 2018-10-18 2021-02-02 万华化学集团股份有限公司 一种聚氨酯催化剂及其制备方法，以及一种聚氨酯喷涂硬质泡沫、一种聚氨酯软质泡沫

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Also Published As

Publication number Publication date
EP0469545A3 (en) 1992-09-16
US5374666A (en) 1994-12-20
DE69122574D1 (de) 1996-11-14
DE69122574T2 (de) 1997-02-20
EP0469545A2 (fr) 1992-02-05

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